JPS63132912A - Curable resin composition - Google Patents
Curable resin compositionInfo
- Publication number
- JPS63132912A JPS63132912A JP28152686A JP28152686A JPS63132912A JP S63132912 A JPS63132912 A JP S63132912A JP 28152686 A JP28152686 A JP 28152686A JP 28152686 A JP28152686 A JP 28152686A JP S63132912 A JPS63132912 A JP S63132912A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- resin composition
- meth
- curable resin
- reaction product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 38
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- SQNMHJHUPDEXMS-UHFFFAOYSA-N 4-(1,2-dicarboxyethyl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C(C(CC(=O)O)C(O)=O)CC(C(O)=O)C(C(O)=O)C2=C1 SQNMHJHUPDEXMS-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 40
- 230000000704 physical effect Effects 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- FFKSVVOWOROQIU-UHFFFAOYSA-N 4-(2,5-dioxooxolan-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Chemical compound C12=CC=CC=C2C(C(O)=O)C(C(=O)O)CC1C1CC(=O)OC1=O FFKSVVOWOROQIU-UHFFFAOYSA-N 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 21
- -1 azide compounds Chemical class 0.000 description 18
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical class CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- UEHUZQKLOWYOMO-UHFFFAOYSA-N diethylazanium;acetate Chemical compound CC(O)=O.CCNCC UEHUZQKLOWYOMO-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- NCIDKUDOSHBPMB-UHFFFAOYSA-N n-methylmethanamine;sulfuric acid Chemical compound CNC.OS(O)(=O)=O NCIDKUDOSHBPMB-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JUVGLPRIQOJMIR-UHFFFAOYSA-N oxiran-2-ylmethyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OCC1CO1 JUVGLPRIQOJMIR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規な硬化性樹脂組成物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel curable resin composition.
［従来の技術］
近年、光硬化性樹脂は種々の分野において広く研究され
、種々のものが実用化されている。これは光硬化性樹脂
が従来の熱硬化型、溶剤溶解型樹脂に比べて、生産性、
省エネルギー性、無公害性等の観点において多くの利点
を有しているためである。[Prior Art] In recent years, photocurable resins have been widely studied in various fields, and various products have been put into practical use. This means that photocurable resins have higher productivity and
This is because it has many advantages in terms of energy saving, non-pollution, etc.
一般に光硬化性樹脂は、感光性基の種類により桂皮酸エ
ステル等の光二量化型、アクリル酸エステル等の光重合
型、アジド化合物等の光分解型等に分類されるが、なか
でも光重合型のアクリル酸エステル系は硬化性、皮膜物
性ともに優れた性能を有することにより最も広く用いら
れている。In general, photocurable resins are classified into photodimerizable types such as cinnamic acid esters, photopolymerizable types such as acrylic esters, and photodegradable types such as azide compounds, depending on the type of photosensitive group. The acrylic ester type is the most widely used because it has excellent performance in both curability and film properties.
又、アクリル酸エステル系の光硬化性樹脂は、高分子量
のアクリルオリゴマーに反応性希釈剤としてアクリルモ
ノマーを加えたものを主成分とし、必要に応じて光重合
開始剤、増感剤、その伯各種の添加剤を加えた形で用い
られる。Acrylic acid ester-based photocurable resins are mainly composed of high molecular weight acrylic oligomers and acrylic monomers as reactive diluents, and optionally contain photopolymerization initiators, sensitizers, and their components. It is used with various additives added.
ここで、公知のアクリルオリゴマーとしては、ポリエス
テルアクリレート、エポキシアクリレート、ウレタンア
クリレート、ポリエーテルアクリレート、アクリルアク
リレート、アルキッドアクリレート等が挙げられるが、
なかでもポリエステルアクリレートは安価でかつバラン
スのよい性能を示すことにより最も広く用いられている
。Here, examples of known acrylic oligomers include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, acrylic acrylate, alkyd acrylate, etc.
Among them, polyester acrylate is the most widely used because it is inexpensive and exhibits well-balanced performance.
［発明が解決しようとする問題点］゛
しかしながら、一般にアクリルオリゴマーを主成分とす
る光硬化性樹脂組成物は金属等との接着性が悪く、又、
接着性を改善しようとすると硬度、機械的強度の低下は
避Ｃノ難く、総合的に満足し得る皮膜物性を有するアク
リルオリゴマーは未だ見い出されていない。又、有機多
価カルボン酸系のポリエステルアクリレートを主成分と
する光硬化性樹脂組成物は、得られる硬化物の物性には
優れるものの、特に空気存在下における硬化速度が遅い
という欠点を有している。[Problems to be solved by the invention] ``However, photocurable resin compositions containing acrylic oligomers as a main component generally have poor adhesion to metals, etc.
When trying to improve adhesion, a decrease in hardness and mechanical strength is unavoidable, and an acrylic oligomer with comprehensively satisfactory film properties has not yet been found. In addition, although photocurable resin compositions containing organic polycarboxylic acid-based polyester acrylate as a main component have excellent physical properties of the resulting cured product, they have the drawback of slow curing speed, especially in the presence of air. There is.
本発明者らは、光硬化性に優れ、かつ硬度、機械的強度
等の物性を低下させることなく金属等との接着性の改善
された硬化性樹脂組成物を開発すべく鋭意研究を重ねた
結果、３，４−ジカルボキシ−１，２，３，４−テトラ
ヒドロ−１−ナフタレンコハク酸（以下ｒＴＤＡＪと称
する）又はその−若しくは二無水物（ＴＤＡとその酸無
水物を総称して、以下ｒＴＤＡ類」と称する）を原料と
して得られるアクリル系化合物から得られる硬化物が、
金属との接着性に優れ、かつ高い硬度及び機械的強度を
示し、更に驚くべきことには、従来のアクリルオリゴマ
ー以上の、空気存在下での硬化性、耐熱性、可撓性、貯
蔵安定性を示すことを見い出し、この知見に基づいて本
発明を完成するに至った。The present inventors have conducted intensive research to develop a curable resin composition that has excellent photocurability and improved adhesion to metals without reducing physical properties such as hardness and mechanical strength. As a result, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid (hereinafter referred to as rTDAJ) or its dianhydride (TDA and its acid anhydride are collectively referred to as below) A cured product obtained from an acrylic compound obtained using acrylic compounds (rTDA) as a raw material is
It has excellent adhesion to metals, high hardness and mechanical strength, and surprisingly, it has better curability in the presence of air, heat resistance, flexibility, and storage stability than conventional acrylic oligomers. The present invention was completed based on this finding.
即ら、本発明はＴＤＡ類と、少なくとも１個のエチレン
性不飽和基を有し、かつ水酸基若しくはグリシジル基を
有する化合物との反応生成物を硬化性成分として含有す
ることを特徴とする新規な硬化性樹脂組成物を提供する
ことを目的とする。That is, the present invention is a novel method comprising, as a curable component, a reaction product of TDA and a compound having at least one ethylenically unsaturated group and a hydroxyl group or a glycidyl group. The purpose is to provide a curable resin composition.
［問題点を解決するための手段］
本発明に係る硬化性化合物は、ＴＤＡ類と、少なくとも
１個のエチレン性不飽和基を有し、かつ水ｍ基若しくは
グリシジル基を有する化合物とを公知の触媒及び熱重合
禁止剤の存在下で、溶媒又は非溶媒系にて５０〜１５０
℃で数時間加熱することにより合成することができる。[Means for Solving the Problems] The curable compound according to the present invention is a combination of TDA and a compound having at least one ethylenically unsaturated group and a water group or a glycidyl group. 50-150 in a solvent or non-solvent system in the presence of a catalyst and a thermal polymerization inhibitor.
It can be synthesized by heating at ℃ for several hours.
少なくとも１個のエチレン性不飽和基を有し、かつ水１
基を有する化合物としては、例えば２−とドロキシエチ
ル（メタ）アクリレート、２−ヒドロキシプロピル（メ
タ）アクリレート、ポリエチレングリコール（メタ）ア
クリレート、トリメチロールプロパン（メタ）アクリレ
ート、ペンタエリスリトール（メタ）アクリレート、ビ
スフェノール型のエポキシ（メタ）アクリレート、２−
ヒドロキシエチルシンナメート等が挙げられる。has at least one ethylenically unsaturated group and 1 water
Examples of compounds having groups include 2- and droxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, trimethylolpropane (meth)acrylate, pentaerythritol (meth)acrylate, and bisphenol type. epoxy (meth)acrylate, 2-
Examples include hydroxyethyl cinnamate.
又、少なくとも１ｆｌ！ｌのエチレン性不飽和基を有し
、かつグリシジル基を有する化合物としては、グリシジ
ル（メタ）アクリレート、グリシジルシンナメート、エ
ポキシステアリル（メタ）アクリレート、ビスフェノー
ルＡ型又はビスフェノールＦ型エポキシの２個のグリシ
ジル基の１個が（メタ）アクリレート化された化合物等
が例示される。Also, at least 1fl! Examples of compounds having an ethylenically unsaturated group of 1 and a glycidyl group include glycidyl (meth)acrylate, glycidyl cinnamate, epoxy stearyl (meth)acrylate, bisphenol A type or bisphenol F type epoxy. Examples include compounds in which one of the groups is (meth)acrylated.
これらの化合物は単独で用いても２種以上混合して用い
てもよく、又、未反応のまま残る過剰分はそのまま硬化
性樹脂組成物中の反応性希釈剤として用いることも出来
る。These compounds may be used alone or in combination of two or more, and the excess remaining unreacted can be used as is as a reactive diluent in the curable resin composition.
この反応は無触媒でも可能であるが、工業的には適当な
触媒を加えるのがより好ましい。用いられる触媒として
は硫酸、リン酸、ｐ−トルエンスルホン酸等の酸触媒、
トリエチルアミン、トリエタノールアミン、Ｎ、Ｎ−ジ
メチルアニリン等の第３級アミン、ジエチルアミン塩酸
塩、ジエチルアミン酢酸塩、ジメチルアミン硫酸塩等の
アミン塩等が挙げられ、その使用聞は、０．０１〜１０
重最％、重量しくは０．１〜５重Ｑ％でおる。This reaction can be carried out without a catalyst, but from an industrial perspective it is more preferable to add a suitable catalyst. Catalysts used include acid catalysts such as sulfuric acid, phosphoric acid, and p-toluenesulfonic acid;
Examples include tertiary amines such as triethylamine, triethanolamine, N,N-dimethylaniline, and amine salts such as diethylamine hydrochloride, diethylamine acetate, and dimethylamine sulfate.
The maximum weight percentage is 0.1 to 5 weight Q%.
熱重合禁止剤としてはベンゾキノン、ナフ：〜キノン等
の゛キノン類、ハイドロキノン、ハイドロキノンモノメ
ヂルエーテル、ｐ −ｔｅｒｔ−ブチルカテコール等の
フェノール類、ナフテン酸銅等の金属塩等が挙げられ、
その添加量は、０．００５〜０゜１重量％、好ましくは
０．０１〜０．０３重量％である。又、重合を抑制する
ためには、更に反応系へ空気等の酸素を含有するガスを
少量ずつ供給しながら反応を行なう方法も有効である。Examples of thermal polymerization inhibitors include quinones such as benzoquinone and naph:-quinone, phenols such as hydroquinone, hydroquinone monomedyl ether, p-tert-butylcatechol, and metal salts such as copper naphthenate.
The amount added is 0.005 to 0.1% by weight, preferably 0.01 to 0.03% by weight. In order to suppress polymerization, it is also effective to carry out the reaction while supplying a gas containing oxygen such as air little by little to the reaction system.
又、溶媒を使用する場合には、ベンゼン、トルエン、ク
ロルベンゼン、１．４−ジオキサン等の不活性溶媒を用
いて反応１ｆｆｌ去する方法、トリメチロールプロパン
トリ（メタ）アクリレート等の上記反応条件下で不活性
な硬化性化合物を用いて、反応侵も除去せずそのまま硬
化性樹脂組成物中の反応性希釈剤とする方法等が挙げら
れる。When using a solvent, use an inert solvent such as benzene, toluene, chlorobenzene, or 1,4-dioxane to remove 1 ffl from the reaction, or use trimethylolpropane tri(meth)acrylate under the above reaction conditions. Examples include a method in which an inactive curable compound is used as a reactive diluent in a curable resin composition without removing the reactive compound.
本発明に係る硬化性樹脂組成物は、以上のようにして得
られた硬化性化合物に必要に応じて反応性希釈剤、重合
開始剤、増感剤等を配合することにより得られる。The curable resin composition according to the present invention can be obtained by blending a reactive diluent, a polymerization initiator, a sensitizer, etc. as necessary with the curable compound obtained as described above.
反応性希釈剤としては、２−エチルヘキシル（メタ）ア
クリレート、ラウリル（メタ）アクリレート、２−ヒド
ロキシエチル（メタ）アクリレート、２−ヒドロキシプ
ロピル（メタ）アクリレ−ｌ−、シクロヘキシル（メタ
）アクリレート、テトラヒドロフルフリル（メタ）アク
リレート、フェノキシエチル（メタ）アクリレ−１〜、
エチレングリコールジ（メタ）アクリレート、ジエチレ
ングリコールジ（メタ）アクリレート、トリエチレング
リコールジ（メタ）アクリレート、ポリエチレングリコ
ールジ（メタ）アクリレート、プロビレングリコールジ
（メタ）アクリレート、ジプロピレングリコールジ（メ
タ）アクリレート、トリプロピレングリコールジ（メタ
）アクリレート、ポリプロピレングリコールジ（メタ）
アクリレート、１．３−ブタンジオールジ（メタ）アク
リレート、１．４−ブタンジオールジ（メタ）アクリレ
ート、１．６−ヘキサンシオールジ（メタ）アクリレー
ト、ネオペンチルグリコールジ（メタ）アクリレート、
ヒドロキシピバリン酸エステルネオペンチルグリコール
ジ（メタ）アクリレ−１〜、トリメチロールプロパント
リ（メタ）アクリレート、ペンタエリスリトールトリ（
メタ）アクリレート、ジペンタエリスリトールヘキサ（
メタ）アクリレ−１〜、ジアリルフタレート、トリアリ
ルシアヌレート、Ｎ−ビニルピロリドン、酢酸ビニル、
スチレン、ビニルトルエン等が挙げられ、その配合量は
、当該硬化性化合物１００ｆｆ１１部に対して１００重
量部以下、好ましくは５０Ｉｆｆｉ部以下である。Reactive diluents include 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate-l-, cyclohexyl (meth)acrylate, and tetrahydrofuryl furyl (meth)acrylate, phenoxyethyl (meth)acrylate-1~,
Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, Tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)
Acrylate, 1.3-butanediol di(meth)acrylate, 1.4-butanediol di(meth)acrylate, 1.6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
Hydroxypivalic acid ester neopentyl glycol di(meth)acrylate-1~, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(
meth)acrylate, dipentaerythritol hexa(
meth)acryle-1~, diallyl phthalate, triallyl cyanurate, N-vinylpyrrolidone, vinyl acetate,
Examples include styrene and vinyltoluene, and the amount thereof is 100 parts by weight or less, preferably 50 Ifi parts or less, based on 11 parts of 100ff of the curable compound.
重合開始剤としては、例えばベンゾインエチルエーテル
、ベンゾフェノン、２．２−ジェトキシアセトフェノン
、ベンジルジメチルケタール、２−エチルア゛ンスラキ
ノン、ミヒラーズケトン等の光重合開始剤、ベンゾイル
パーオキサイド、ジクミルパーオキサイド、ｔｅｒｔ−
ブチルパーベンゾエート等の各種過酸化物、アゾビスイ
ソブチロニトリル、フェニルアセトアルデヒド等の熱重
合開始剤が掲げられる。Examples of the polymerization initiator include photopolymerization initiators such as benzoin ethyl ether, benzophenone, 2,2-jetoxyacetophenone, benzyl dimethyl ketal, 2-ethyl athraquinone, and Michler's ketone, benzoyl peroxide, dicumyl peroxide, and tert-
Examples include various peroxides such as butyl perbenzoate, thermal polymerization initiators such as azobisisobutyronitrile, and phenylacetaldehyde.
又、増感剤としては、例えば光硬化の場合にはトリエチ
ルアミン、トリエチレンテトラミン等のアミン類、アリ
ルチオ尿素等の尿素類、ナｌ−リウムジエチルジチオホ
スフエート等の硫黄化合物、Ｎ、Ｎ−ジメチル−ｐ−ア
ミノベンゾニトリル等のニトリル類、トリーｎ−ブチル
ホスフィン等のリン化合物等が掲げられる。又、熱硬化
、常温硬化の場合にはナフテン酸コバルト、ナフテン酸
マンガン等の金属塩類、Ｎ、Ｎ−ジメチルアニリン、Ｎ
、Ｎ−ジメチル−ｐ−トルイジン等の芳香族第３級アミ
ン類等の上記各種過酸化物とレドックス触媒系を形成す
る化合物が挙げられる。In addition, as a sensitizer, for example, in the case of photocuring, amines such as triethylamine and triethylenetetramine, ureas such as allylthiourea, sulfur compounds such as sodium diethyldithiophosphate, N,N-dimethyl Examples include nitriles such as -p-aminobenzonitrile, phosphorus compounds such as tri-n-butylphosphine, and the like. In addition, in the case of heat curing or room temperature curing, metal salts such as cobalt naphthenate and manganese naphthenate, N,N-dimethylaniline, N
, aromatic tertiary amines such as N-dimethyl-p-toluidine, and other compounds that form a redox catalyst system with the above various peroxides.
上記夫々の配合量は、硬化性成分１００重聞１に対して
０．０１〜２０重量部、好ましくは０゜１〜１０重量部
の範囲である。The amount of each of the above compounds is in the range of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts of the curable component.
更に、本発明に係る硬化性樹脂組成物には必要に応じて
伯の反応性オリゴマーや充填剤、着色剤、レベリング剤
、′可塑剤等の各種添加剤を適宜加えることができる。Furthermore, various additives such as reactive oligomers, fillers, colorants, leveling agents, and plasticizers can be added to the curable resin composition according to the present invention, if necessary.
本発明に係る硬化性樹脂組成物は、光や熱によって速や
かに硬化することができる外、電子線、放射線等の電離
性放射線を照射して硬化させることも可能であり、その
場合には前述の重合開始剤、増感剤は必ずしも加える必
要はない。The curable resin composition according to the present invention can be rapidly cured by light or heat, and can also be cured by irradiation with ionizing radiation such as electron beams or radiation. It is not always necessary to add a polymerization initiator and a sensitizer.
［発明の効果］
かくして得られた硬化物は、高い硬度、機械的強度、耐
熱性を有し、更に金属との接着性、可撓性に優れるため
、塗料、接着剤、印刷インキ、製版材料、電気部品のシ
ーリング剤、ポツティング剤等の各種用途に好適である
。[Effect of the invention] The cured product thus obtained has high hardness, mechanical strength, and heat resistance, and also has excellent adhesion to metals and flexibility, so it can be used as a paint, adhesive, printing ink, or plate-making material. It is suitable for various uses such as sealing agent for electrical parts and potting agent.
又、本発明に係る硬化性化合物は、従来の硬化性樹脂組
成物中に添加することにより、硬化性、接着性、耐熱性
、貯蔵安定性等の特性の改善を図ることができる。Furthermore, by adding the curable compound according to the present invention to a conventional curable resin composition, it is possible to improve properties such as curability, adhesiveness, heat resistance, and storage stability.
［実施例コ 以下に実施例を掲げ、本発明の詳細な説明する。[Example code] The present invention will be described in detail below with reference to Examples.
実施例１
ＴＤＡ二無水物１５０９．２−ヒドロキシエチルアクリ
レート２３０９、トリエチルアミン０゜３８３、ハイド
ロキノンモノメチルエーテル０゜０６８！？の夫々を反
応容器中に仕込み、７５℃で５時間反応を行ない、無色
透明な液体状の反応生成物を得た。Example 1 TDA dianhydride 1509.2-hydroxyethyl acrylate 2309, triethylamine 0°383, hydroquinone monomethyl ether 0°068! ? Each of these was charged into a reaction vessel and reacted at 75°C for 5 hours to obtain a colorless and transparent liquid reaction product.
得られた反応生成物１００＠１部に２，２−ジェトキシ
アセトフェノン３重量部を配合し、硬化性樹脂組成物を
調製した。得られた硬化性樹脂組成物の回転粘度、硬化
時間、及びその硬化物の鉛筆硬度、密着性、耐屈曲性を
測定し、その結果を第１表に示した。なお、各物性値の
測定方法は下記の通りである。3 parts by weight of 2,2-jethoxyacetophenone was blended with 100@1 part of the obtained reaction product to prepare a curable resin composition. The rotational viscosity and curing time of the obtained curable resin composition, as well as the pencil hardness, adhesion, and bending resistance of the cured product were measured, and the results are shown in Table 1. The method for measuring each physical property value is as follows.
１献呈痕 Ｅ型回転粘度計を用いて、３０℃で測定した。1 dedication mark Measurement was performed at 30°C using an E-type rotational viscometer.
鼠生田層
ブリキ板上にＢ形フィルムアプリケーターを用いて硬化
性樹脂組成物を塗布し、空気中で１００Ｗの高圧水銀灯
を用いて、１０傭の距離から紫外線を照射し、塗膜表面
の指触屹燥時間を測定した。A curable resin composition was applied onto the tin plate using a B-type film applicator, and ultraviolet rays were irradiated from a distance of 10 minutes using a 100W high-pressure mercury lamp in the air, and the surface of the coating film was touched with the finger. The drying time was measured.
糺至四瓜
鋼板上に塗布した５硬化性樹脂組成物を１００Ｗ−１０
ｃｒｎの高圧水銀灯で６０秒間光硬化した。得られた硬
化膜（厚さ約５０μ〉をＪＩＳ−に５４００の「鉛筆引
っかき試験」に準拠して測定した。5 curable resin composition applied on a tenacious steel plate at 100W-10
It was photocured for 60 seconds using a CRN high pressure mercury lamp. The obtained cured film (thickness: approximately 50 μm) was measured in accordance with JIS-5400 “Pencil Scratch Test”.
扉塁且
鉛筆硬度測定の場合と同様にして得られた硬化膜に縦横
各１５１１＋１間隔で切れ目を入れて１００個の基盤目
をつくり、次いでセロファンテープはぎを行ない、鋼板
上に残った基盤目の数を測定した。The cured film obtained in the same manner as in the case of the door base and pencil hardness measurement was cut vertically and horizontally at intervals of 1511+1 to create 100 base holes.Then, the cellophane tape was removed and the base holes remaining on the steel plate were removed. The number was measured.
鮭皿助１
ブリキ板上に塗布した硬化性樹脂組成物を１００Ｗ−’
ｌ０ｃｔｎの高圧水銀灯で６０秒問光硬化した。Salmon Sarasuke 1 A curable resin composition coated on a tin plate at 100W-'
It was photocured for 60 seconds using a 10 ctn high pressure mercury lamp.
得られた硬化膜の耐屈曲性をＪＩＳ−に５４００に準拠
して測定した。The bending resistance of the obtained cured film was measured in accordance with JIS-5400.
実施例２
ＴＤＡ二無水物１５０ｇ、２−とドロキシエチルアクリ
レート１８２．５ｆｆ、トリエチルアミン０．３３ｇ、
ハイドロキノンモノメチルエーテル０．０６４ｇの夫々
を反応容器中に仕込み、７５℃で５時間反応を行ない、
無色透明な液体状の反応生成物を得た。Example 2 150 g of TDA dianhydride, 182.5 ff of 2- and droxyethyl acrylate, 0.33 g of triethylamine,
0.064 g of each hydroquinone monomethyl ether was charged into a reaction vessel, and the reaction was carried out at 75°C for 5 hours.
A colorless and transparent liquid reaction product was obtained.
得られた反応生成物より実施例１と同様にして硬化性樹
脂組成物を調製し、その物性を測定した。A curable resin composition was prepared from the obtained reaction product in the same manner as in Example 1, and its physical properties were measured.
その結果を第１表に示す。The results are shown in Table 1.
実施例３
ＴＤＡ二無水物１５０３．２−ヒドロキシエチルアクリ
レート１２１．８ｇ、１．６−ヘキサンジオールジアク
リレート１０８．２ｇ、トリエチルアミン０．３８９、
ハイドロキノンモノメチルエーテル０．０６４ｇの夫々
を反応容器中に仕込み、７５℃で７時間反応を行ない、
無色透明な液体状の反応生成物を１ｑだ。Example 3 TDA dianhydride 1503.2-hydroxyethyl acrylate 121.8 g, 1,6-hexanediol diacrylate 108.2 g, triethylamine 0.389,
0.064 g of each hydroquinone monomethyl ether was charged into a reaction vessel, and the reaction was carried out at 75°C for 7 hours.
1q of colorless and transparent liquid reaction product.
得られた反応生成物より実施例１と同様にして硬化性樹
脂組成物を調製し、その物性を測定した。A curable resin composition was prepared from the obtained reaction product in the same manner as in Example 1, and its physical properties were measured.
その結果を第１表に示す。The results are shown in Table 1.
実施例４
ＴＤＡ二無水物１５０９．２−ヒドロキシエチルアクリ
レート１２１．８ｇ、トリメチロールプロパントリアク
リレート７２．１．２−エチルへキシルアクリレート３
６．１ｇ、トリエチルアミン０．３８ｇ、ハイドロキノ
ンモノメチルエーテル０．０６ｇの夫々を反応容器中に
仕込み、７５℃で７時間反応を行ない、無色透明な液体
状の反応生成物を得た。Example 4 TDA dianhydride 1509.2-hydroxyethyl acrylate 121.8g, trimethylolpropane triacrylate 72.1.2-ethylhexyl acrylate 3
6.1 g of triethylamine, 0.38 g of hydroquinone monomethyl ether, and 0.06 g of hydroquinone monomethyl ether were charged into a reaction vessel, and the reaction was carried out at 75° C. for 7 hours to obtain a colorless and transparent liquid reaction product.
得られた反応生成物より実施例１と同様にして硬化性樹
脂組成物を調製し、その物性を測定した。A curable resin composition was prepared from the obtained reaction product in the same manner as in Example 1, and its physical properties were measured.
その結果を第１表に示す。The results are shown in Table 1.
実施例５
ＴＤＡ二無水物１５０ｇ、２−とドロキシエチルアクリ
レート２００．３９、トリエチルアミン０．４２ｇ、ハ
イドロキノンモノメチルエーテル０．０７９の夫々を反
応容器中に仕込み、７５℃で５時間反応を行なった。冷
却後、グリシジルメタクリレート７１ｇを仕込み、更に
９５℃で５時間反応を行ない、無色透明な液体状の反応
生成物を得た。Example 5 150 g of TDA dianhydride, 200.39 g of 2-droxyethyl acrylate, 0.42 g of triethylamine, and 0.079 g of hydroquinone monomethyl ether were charged into a reaction vessel and reacted at 75° C. for 5 hours. After cooling, 71 g of glycidyl methacrylate was charged, and the reaction was further carried out at 95° C. for 5 hours to obtain a colorless and transparent liquid reaction product.
得られた反応生成物より実施例１と同様にして硬化性樹
脂組成物を調製し、その物性を測定した。A curable resin composition was prepared from the obtained reaction product in the same manner as in Example 1, and its physical properties were measured.
その結果を第１表に示す。The results are shown in Table 1.
実施例６
ＴＤＡ二無水物１２０９を反応容器中に仕込み、窒素雰
囲気下２００℃で溶融後、トリエチレングリコール３０
びを滴下し、２時間反応を行ない、融点１０９〜１１２
℃の淡黄色の反応生成物を得た。次に、当該反応生成物
１５０ｇ、２−ヒドロキシエチルアクリレート１３０．
６ｇ、トリエチルアミン０．２８ｇ、ハイドロキノンモ
ノメチルエーテル０．０６ｇの夫々を反応容器中に仕込
み、７５℃で５時間反応を行ない、淡黄色透明な液体状
の反応生成物を得た。この反応生成物より実施例１と同
様にして硬化性樹脂組成物を調製し、その物性を測定し
た。その結果を第１表に示す。Example 6 TDA dianhydride 1209 was charged into a reaction vessel, and after melting at 200°C under nitrogen atmosphere, triethylene glycol 30
was added dropwise and reacted for 2 hours to obtain a melting point of 109-112.
A pale yellow reaction product was obtained. Next, 150 g of the reaction product, 130 g of 2-hydroxyethyl acrylate.
6g of triethylamine, 0.28g of triethylamine, and 0.06g of hydroquinone monomethyl ether were charged into a reaction vessel, and the reaction was carried out at 75°C for 5 hours to obtain a pale yellow transparent liquid reaction product. A curable resin composition was prepared from this reaction product in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 1.
実施例７
実施例２で得られた反応生成物７５重量部に汎用ポリエ
ステルアクリレート（無水フタル酸−ネオベンチルグリ
コール系）２５重ｆｉｔ部、２，２−ジェトキシアセト
フェノン３重量部を配合し、硬化性樹脂組成物を調製し
た。得られた硬化性樹脂組成物の物性を実施例１と同様
にして測定した。Example 7 25 parts by weight of general-purpose polyester acrylate (phthalic anhydride-neobentyl glycol type) and 3 parts by weight of 2,2-jethoxyacetophenone were blended with 75 parts by weight of the reaction product obtained in Example 2, A curable resin composition was prepared. The physical properties of the obtained curable resin composition were measured in the same manner as in Example 1.
その結果を第１表に示す。The results are shown in Table 1.
実施例８
実施例２で得られた反応生成物６２，５重量部に汎用ポ
リエステルアクリレート３７．５重里部、２．２−ジェ
トキシアセトフェノン３重量部を配合し、硬化性樹脂組
成物を調製した。得られた硬化性樹脂組成物の物性を実
施例１と同様にして測定した。その結果を第２表に示す
。Example 8 62.5 parts by weight of the reaction product obtained in Example 2 was blended with 37.5 parts by weight of general-purpose polyester acrylate and 3 parts by weight of 2,2-jetoxyacetophenone to prepare a curable resin composition. . The physical properties of the obtained curable resin composition were measured in the same manner as in Example 1. The results are shown in Table 2.
実施例９
実施例２で得られた反応生成物５０重量部に汎用エポキ
シアクリレート（ビスフェノールＡ型）４０重ｆｆ１部
、２，２−ジェトキシアセトフェノン３重色部を配合し
、硬化性樹脂組成物を調製した。Example 9 50 parts by weight of the reaction product obtained in Example 2 were blended with 1 part of 40 parts of general-purpose epoxy acrylate (bisphenol A type) and 3 parts of 2,2-jetoxyacetophenone to form a curable resin composition. was prepared.
得られた硬化性樹脂組成物の物性を実施例１と同様にし
て測定した二その結果を第２表に示す。The physical properties of the obtained curable resin composition were measured in the same manner as in Example 1. The results are shown in Table 2.
比較例１
無水フタル［１４８９，２−ヒドロキシエチルアクリレ
ート１２１．８９、トリエチルアミン０゜２７９、ハイ
ドロキノンモノメチルエーテル００Ｏ５６９の夫々を反
応容器中に仕込み、７５℃で７時間反応を行なったとこ
ろ、白く濁った液体状の反応生成物が得られた。この反
応生成物より実施例１と同様に硬化性樹脂組成物を調製
し、その物性を測定した。その結果を第２表に示す。Comparative Example 1 Anhydrous phthalic [1489, 2-hydroxyethyl acrylate 121.89, triethylamine 0.279, and hydroquinone monomethyl ether 00O569] were charged into a reaction vessel and reacted at 75°C for 7 hours, resulting in a white cloudy liquid. A reaction product was obtained. A curable resin composition was prepared from this reaction product in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 2.
比較例２
無水ピロメリット酸１０９ｇ、２−ヒドロキシエチルア
クリレート２６６９、トリエチルアミン０．３８ｇ、ハ
イドロキノンモノメチルエーテル０．０６ＳＦを反応容
器中に仕込み、７５℃で５時間反応を行ない、黄色透明
な液体状の反応生成物を得た。この反応生成物より実施
例１と同様に硬化性樹脂組成物を調製し、その物性を測
定した。Comparative Example 2 109g of pyromellitic anhydride, 2669g of 2-hydroxyethyl acrylate, 0.38g of triethylamine, and 0.06SF of hydroquinone monomethyl ether were charged into a reaction vessel, and the reaction was carried out at 75°C for 5 hours to form a yellow transparent liquid reaction. The product was obtained. A curable resin composition was prepared from this reaction product in the same manner as in Example 1, and its physical properties were measured.
その結果を第２表に示す。The results are shown in Table 2.
比較例３
汎用ポリエステルアクリレート１００型組部に２．２−
ジェトキシアセトフェノン３重量部を配合し、硬化性樹
脂組成物を［１した。得られた硬化性樹脂組成物を実施
例１と同様にして測定した。Comparative Example 3 2.2-
3 parts by weight of jetoxyacetophenone was blended to prepare a curable resin composition. The obtained curable resin composition was measured in the same manner as in Example 1.
その結果を第２表に示す。The results are shown in Table 2.
比較例４
汎用エポキシアクリレート８０重量部に２−ヒドロキシ
エチルアクリレート２０重ｆｆ１部、２，２−ジェトキ
シアセトフェノン３重量部を配合し、硬化性樹脂組成物
を調製した。得られた硬化性樹脂組成物を実施例１と同
様にして測定した。その結果を第２表に示す。Comparative Example 4 A curable resin composition was prepared by blending 80 parts by weight of general-purpose epoxy acrylate with 1 part by weight of 20 parts by weight of 2-hydroxyethyl acrylate and 3 parts by weight of 2,2-jethoxyacetophenone. The obtained curable resin composition was measured in the same manner as in Example 1. The results are shown in Table 2.
比較例５
汎用ウレタンアクリレート８０重量部に２−ヒドロキシ
エチルアクリレート２０１ｆｔ部、２．２−ジェトキシ
アセトフェノン３重量部を配合し、硬化性樹脂組成物を
調製した。得られた硬化性樹脂組成物を実施例１と同様
にして測定した。その結果を第２表に示す。Comparative Example 5 201 ft parts of 2-hydroxyethyl acrylate and 3 parts by weight of 2,2-jethoxyacetophenone were blended with 80 parts by weight of general-purpose urethane acrylate to prepare a curable resin composition. The obtained curable resin composition was measured in the same manner as in Example 1. The results are shown in Table 2.
なお、第１表及び第２表中の各略記号は、各々次の化合
物を記す。In addition, each abbreviation in Tables 1 and 2 represents the following compounds.
ＴＤＡ−２ＨＥＡ＝３．４−ジカルボキシ−１゜２．３
．４−テトラヒドロ−１−ナフタレンコハク酸ジアクリ
ロイルオキシエチルエステルＴＤＡ−２ＨＥＡ−１ＧＭ
Ａ＝３．４−シカルボキシ−１，２，３，４−テトラヒ
ドロ−１−ナフタレンコハタ酸ジアクリロイルオキシエ
チルモノ−２−ヒドロキシ−３−メタクリロイルオキシ
エチルエステル
ＨＥＡ＝２−ヒドロキシエチルアクリレートＨＤＤＡ＝
１．６−ヘキサンジオールジアクリレート
丁ＭＰＴＡ＝トリメチロールプロパントリアクリレート
ＥＨＡ＝２−エチルへキシルアクリレートＤＥＡＰ＝２
．２−ジェトキシアセトフェノンＴＥＧ変性ＴＤＡ−２
ＨＥＡ＝ＴＤＡ−２ＨＥＡのトリエチレングリコール変
性物
ＰＡ−１ＨＥＡ＝フタル酸モノアクリロイルオキシエチ
ルエステル
ＰＭＤＡ−２ＨＥＡ＝ピロメリツト酸ジアクリロイルオ
キシエチルエステル
手続補正書く自発）
昭和６３年２月２３日
特許庁長官 小 川 邦 夫 殿 撞１
、事件の表示
昭和６１年特願昭第２８１５２６号
２、発明の名称
硬化性樹脂組成物
３、補正をする者
事件との関係 特許出願人
名称 新日本理化株式会社 （πＬ ０７５−６１１−
２２０１）５、補正の対象
明細書中「発明の詳細な説明」の欄
ｉ正の内容 ５！ｌ１ＭＷ［ｄの；翻 ｒ
≧＼補正の内容
１．明細書第１０真下から第７行目に記載の「好適であ
る。」を
［好適である。TDA-2HEA=3.4-dicarboxy-1°2.3
．． 4-tetrahydro-1-naphthalenesuccinic acid diacryloyloxyethyl ester TDA-2HEA-1GM
A=3.4-Cycarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinate diacryloyloxyethyl mono-2-hydroxy-3-methacryloyloxyethyl ester HEA=2-hydroxyethyl acrylate HDDA=
1.6-hexanediol diacrylate MPTA=trimethylolpropane triacrylate EHA=2-ethylhexyl acrylate DEAP=2
．． 2-Jethoxyacetophenone TEG-modified TDA-2
HEA = TDA-2 Triethylene glycol modified product of HEA PA-1 HEA = Phthalic acid monoacryloyloxyethyl ester PMDA-2HEA = Pyromellitic acid diacryloyloxyethyl ester Procedural amendment voluntary) February 23, 1985 Commissioner of the Japan Patent Office Ogawa Kunio Tono 1
, Description of the case Japanese Patent Application No. 281526 of 1985 2 Name of the invention Curable resin composition 3 Person making the amendment Relationship to the case Name of patent applicant Shin Nippon Chemical Co., Ltd. (πL 075-611-
2201) 5. Correct content in column “Detailed Description of the Invention” in the specification to be amended 5! l1MW[d; translation r
≧＼Contents of correction 1. "It is suitable." written in the seventh line from the bottom of No. 10 of the specification means "it is suitable."
更に、本発明に係る硬化性化合物が以下の実施例に示さ
れる如くカルボキシル基を有する場合には、アルカリ水
に可溶であるため、未硬化部分を除去するに際して有機
溶剤を使用する必要がなく、又、アルカリ水処理後の解
像性、耐水性等にも優れており、特に製版材料、レジス
ト、接着剤等として有用である。」と補正する。Furthermore, when the curable compound according to the present invention has a carboxyl group as shown in the examples below, it is soluble in alkaline water, so there is no need to use an organic solvent to remove the uncured portion. It also has excellent resolution and water resistance after treatment with alkaline water, and is particularly useful as plate-making materials, resists, adhesives, and the like. ” he corrected.
以上that's all
Claims (1)
−１−ナフタレンコハク酸又はその酸無水物と少なくと
も１個のエチレン性不飽和基を有し、かつ水酸基若しく
はグリシジル基を有する化合物との反応生成物を硬化性
成分として含有することを特徴とする硬化性樹脂組成物
。3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid or its acid anhydride, and a compound having at least one ethylenically unsaturated group and a hydroxyl group or a glycidyl group. A curable resin composition comprising a reaction product of the following as a curable component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28152686A JPS63132912A (en) | 1986-11-25 | 1986-11-25 | Curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28152686A JPS63132912A (en) | 1986-11-25 | 1986-11-25 | Curable resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63132912A true JPS63132912A (en) | 1988-06-04 |
Family
ID=17640404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28152686A Pending JPS63132912A (en) | 1986-11-25 | 1986-11-25 | Curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63132912A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63312377A (en) * | 1987-06-12 | 1988-12-20 | New Japan Chem Co Ltd | Bonding composition |
-
1986
- 1986-11-25 JP JP28152686A patent/JPS63132912A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63312377A (en) * | 1987-06-12 | 1988-12-20 | New Japan Chem Co Ltd | Bonding composition |
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